Synthesis and Characterization of Acrylate‐Based Block and Block‐Graft Copolymers Using Polyester‐Based Macro‐ RAFT Agents Through Two‐Step Polymerization and Assessment of One‐Pot Epoxy Group Ring‐O

ABSTRACT

This study reports the synthesis of a macro‐RAFT agent based on poly(ɛ‐caprolactone) (PCL) via ring‐opening polymerization (ROP), which was subsequently used to prepare acrylate‐based block and block‐graft copolymers through RAFT polymerization. The macro‐RAFT agent enabled RAFT polymerization of glycidyl methacrylate (GMA) and methyl methacrylate (MMA) under controlled conditions. To determine optimal polymerization parameters, such as temperature, polymerizations were conducted at two different temperatures with both vinyl monomers in the presence of the PCL‐based macro‐RAFT agent. During RAFT polymerization, the epoxy ring of poly(GMA) underwent ring opening, and the hydrogel properties of the resulting copolymer were evaluated as a result of crosslinking. Structural and molecular characteristics were evaluated using nuclear magnetic resonance (NMR) and Fourier‐transform infrared spectroscopy (FTIR). The number‐average molecular weight (Mn) was measured by gel permeation chromatography (GPC). Thermal properties were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The elemental composition of the macro‐RAFT agent was determined using scanning electron microscopy (SEM) and energy‐dispersive x‐ray spectroscopy (EDX).